Heterocyclic azo dyes

ABSTRACT

Novel compounds of the general formula I ##STR1## where X is hydrogen, nitro or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or hetaryl, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, R is unsubstituted or substituted alkyl or aryl, R 1  is hydrogen or R 2 , and R 2  is unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl, are useful for dyeing textile fibers, in particular polyesters.

This application is a continuation of application Ser. No. 004,826, filed on Jan. 12, 1987, now abandoned, which is a continuation of application Ser. No. 758,450, filed July 24, 1985.

The present invention relates to compounds of the general formula: ##STR2## where X is hydrogen, nitro or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or hetaryl, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, R is unsubstituted or substituted alkyl or aryl, R¹ is hydrogen or R², and R² is unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl.

X is hydrogen or, for example, C₁ -C₈ -alkyl which may be substituted by chlorine, bromine or phenyl, or thienyl, furyl or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or nitro.

Specific examples of alkyl radicals are: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₈ H₁₇ and ##STR3## the abbreviated formula also embracing the n- and isoradicals. Specific examples of radicals Y in addition to those stated above are: CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, C₄ H₉ CO, C₅ H₁₁ CO, C₇ H₁₅ CO, ##STR4## C₆ H₅ CO, CH₃ C₆ H₄ CO, ClC₆ H₄ CO, (CH₃)₂ C₆ H₃ CO, H₃ COC₆ H₄ CO, Cl₂ C₆ H₃ CO, CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO₂, CH₃ C₆ H₄ SO₂, ClC₆ H₄ SO₂, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, ##STR5## COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ H₉, COOC₆ H₅, COOC₆ H₄ CH₃, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₁₃, CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₄ H₉)₂, ##STR6##

R is, for example, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl, benzyl or phenyl which is mono-substituted or polysubstituted by C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, phenoxy, benzyloxy, phenyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -mono- or dialkylamino, C₁ -C₄ -alkoxyethoxy, C₁ -C₄ -alkylmercapto, phenylmercapto or C₁ -C₅ -alkanoylamino, such as acetylamino, propionylamino, butyrylamino or valerylamino.

In addition to the radicals stated above, R² is, for example, C₁ -C₆ -alkyl which may be substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl, or is phenyl, benzyl, phenethyl or cyclohexyl.

Specific examples of radicals R² are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxyporpyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2- -phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxy-carbonylethyl, 2-propoxyethoxycarbonyleythyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl.

Specific examples of radicals R in addition to those stated above are phenyl, o-, m- and p-methylphenyl, o-, m- and p-ethylphenyl, o-, m- and p-methoxyphenyl, o-, m- and p-ethoxyphenyl, o-, m- and p-chlorophenyl, o-, m- and p-acetylaminophenyl, o-, m- and p-bromophenyl, o-, m- and p-nitrophenyl, (CH₃)₂)C₆ H₃, (C₂ H₅)₂ C₆ H₃, Cl₂ C₆ H₃, o- m- and p-propionylaminophenyl, o-, m- and p-butyrylaminophenyl, o-, m- and p-β-cyanoethoxyphenyl, methyl, ethyl, n- and isopropyl, n-, iso- and sec.-butyl, allyl, methallyl, furyl and thienyl.

The compounds of the formula I have red to blue hues and are particularly useful for dyeing polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers. As a rule, the dyeings obtained have good or very good fastness properties, particularly on polyesters.

The compounds of the formula I can be prepared by reacting a diazonium compound of an amine of the formula ##STR7## with a compound of the formula ##STR8## by a conventional method. The Examples which follow illustrate the preparation. Parts and percentages are by weight, unless stated otherwise.

Of particular importance are compounds of the formula Ia ##STR9##

where X¹ is hydrogen or C₁ -C₄ -alkyl, or is thienyl, furyl or phenyl which is unsubstituted or substituted by methyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro or acylamino, B is phenyl which is unsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkoxy, -cyanoethoxy, methyl, ethyl or C₁ -C₄ -alkanoylamino, and B¹ and B² independently of one another are each benzyl, phenylethyl, cyclohexyl, allyl, chloroallyl, phenyl or C₁ -C₄ -alkyl which is unsubstituted or substituted by hydroxyl, cyano, C₁ -C₄ -alkoxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyloxy or C₁ -C₄ -alkylaminocarbonyloxy, and one of the radicals B¹ or B² may furthermore be hydrogen.

EXAMPLE 1

21.6 parts of 2-amino-3-cyano-4-phenyl-5-formylthiophene were introduced into a mixture of 150 parts of 3:1 glacial acetic acid/propionic acid and 70 parts of 85% strength sulfuric acid. 32 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C., after which the mixture was stirred for 4 hours at this temperature.

24.0 parts of 2-diethylamino-4-phenyl-thiazole were dissolved in 100 parts of dimethylformamide, and the solution was introduced into 400 parts of ice and 2 parts of amidosulfonic acid. The diazo solution obtained previously was added in the course of 2 hours with external cooling with ice/water, and the mixture was stirred overnight without further cooling. The product was filtered off under suction, washed neutral with water and dried at 80° C. in a drying oven under reduced pressure to give 40 parts of a bluish black powder of the formula ##STR10## which dyes polyester fabric in fast royal blue hues.

If 23.9 parts of 2-diethylamino-4-(2'-thienyl)-thiazole are used instead of 24 parts of 2-diethylamino-4-phenylthiazole and the procedure described above is followed, 42 arts of a bluish black powder are obtained, this powder dyeing polyester fibers in fast greenish-blue hues.

The dyes defined in the Table below are also obtained in a similar manner.

    __________________________________________________________________________     DNNK                                                                                                                             Hue on                       Example                                                                             D                   K                        polyester                    __________________________________________________________________________           ##STR11##                                                                                          ##STR12##               blue                         3                                                                                    ##STR13##                                                                                          ##STR14##               greenish blue                4                                                                                    ##STR15##                                                                                          ##STR16##               blue                         5                                                                                    ##STR17##                                                                                          ##STR18##               blue                         6                                                                                    ##STR19##                                                                                          ##STR20##               reddish blue                 7                                                                                    ##STR21##                                                                                          ##STR22##               greenish blue                8                                                                                    ##STR23##                                                                                          ##STR24##               blue                         9                                                                                    ##STR25##                                                                                          ##STR26##               greenish blue                10                                                                                   ##STR27##                                                                                          ##STR28##               greenish blue                11                                                                                   ##STR29##                                                                                          ##STR30##               blue                         12                                                                                   ##STR31##                                                                                          ##STR32##               green                        13                                                                                   ##STR33##                                                                                          ##STR34##               greenish blue                14                                                                                   ##STR35##                                                                                          ##STR36##               blue                         15                                                                                   ##STR37##                                                                                          ##STR38##               greenish blue                16                                                                                   ##STR39##                                                                                          ##STR40##               greenish  blue               17                                                                                   ##STR41##                                                                                          ##STR42##               greenish blue                18                                                                                   ##STR43##                                                                                          ##STR44##               greenish blue                19                                                                                   ##STR45##                                                                                          ##STR46##               greenish blue                20                                                                                   ##STR47##                                                                                          ##STR48##               greenish blue                21                                                                                   ##STR49##                                                                                          ##STR50##               blue                         22                                                                                   ##STR51##                                                                                          ##STR52##               blue                         23                                                                                   ##STR53##                                                                                          ##STR54##               blue                         24                                                                                   ##STR55##                                                                                          ##STR56##               blue                         25                                                                                   ##STR57##                                                                                          ##STR58##               blue                         26                                                                                   ##STR59##                                                                                          ##STR60##               blue                         27                                                                                   ##STR61##                                                                                          ##STR62##               blue                         28                                                                                   ##STR63##                                                                                          ##STR64##               blue                         29                                                                                   ##STR65##                                                                                          ##STR66##               blue                         30                                                                                   ##STR67##                                                                                          ##STR68##               blue                         31                                                                                   ##STR69##                                                                                          ##STR70##               blue                         32                                                                                   ##STR71##                                                                                          ##STR72##               blue                         33                                                                                   ##STR73##                                                                                          ##STR74##               blue                         34                                                                                   ##STR75##                                                                                          ##STR76##               blue                         35                                                                                   ##STR77##                                                                                          ##STR78##               blue                         36                                                                                   ##STR79##                                                                                          ##STR80##               blue                         37                                                                                   ##STR81##                                                                                          ##STR82##               blue                         38                                                                                   ##STR83##                                                                                          ##STR84##               blue                         39                                                                                   ##STR85##                                                                                          ##STR86##               blue                         40                                                                                   ##STR87##                                                                                          ##STR88##               blue                         41                                                                                   ##STR89##                                                                                          ##STR90##               blue                         42                                                                                   ##STR91##                                                                                          ##STR92##               violet                       43                                                                                   ##STR93##                                                                                          ##STR94##               blue                         44                                                                                   ##STR95##                                                                                          ##STR96##               blue                         45                                                                                   ##STR97##                                                                                          ##STR98##               blue                         46                                                                                   ##STR99##                                                                                          ##STR100##              blue                         47                                                                                   ##STR101##                                                                                         ##STR102##              blue                         48                                                                                   ##STR103##                                                                                         ##STR104##              blue                         49                                                                                   ##STR105##                                                                                         ##STR106##              blue                         50                                                                                   ##STR107##                                                                                         ##STR108##              blue                         51                                                                                   ##STR109##                                                                                         ##STR110##              blue                         52                                                                                   ##STR111##                                                                                         ##STR112##              blue                         53                                                                                   ##STR113##                                                                                         ##STR114##              blue                         54                                                                                   ##STR115##                                                                                         ##STR116##              blue                         55                                                                                   ##STR117##                                                                                         ##STR118##              bluish violet                56                                                                                   ##STR119##                                                                                         ##STR120##              blue                         57                                                                                   ##STR121##                                                                                         ##STR122##              blue                         58                                                                                   ##STR123##                                                                                         ##STR124##              blue                         59                                                                                   ##STR125##                                                                                         ##STR126##              blue                         60                                                                                   ##STR127##                                                                                         ##STR128##              greenish blue                61                                                                                   ##STR129##                                                                                         ##STR130##              blue                         62                                                                                   ##STR131##                                                                                         ##STR132##              blue                         63                                                                                   ##STR133##                                                                                         ##STR134##              blue                         64                                                                                   ##STR135##                                                                                         ##STR136##              blue                         65                                                                                   ##STR137##                                                                                         ##STR138##              blue                         __________________________________________________________________________ 

We claim:
 1. A compound of the formula I ##STR139## where X is hydrogen, nitro or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or hetaryl, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, R is unsubstituted or substituted alkyl or aryl, R¹ is hydrogen or R², and R² is unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl.
 2. A compound as claimed in claim 1, of the formula ##STR140## where X¹ is hydrogen or C₁ -C₄ -alkyl or is thienyl, furyl or phenyl which is unsubstituted or substituted by methyl, ethyl, methoxy, ethoxy, chlorine, bromine, nitro or acylamino, B is phenyl which is unsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkoxy, -cyanoethoxy, methyl, ethyl or C₁ -C₄ -alkanoylamino, and B¹ and B² independently of one another are each benzyl, phenylethyl, cyclohexyl, allyl, chloroallyl, phenyl or C₁ -C₄ -alkyl which is unsubstituted or substituted by hydroxyl, cyano, C₁ -C₄ -alkoxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyloxy or C₁ -C₄ -alkylaminocarbonyloxy, and one of the radicals B¹ or B² may furthermore be hydrogen.
 3. The compound of claim 1 wherein X is hydrogen, nitro, C₁ -C₈ alkyl which may be substituted by chlorine, bromine, or phenyl; or phenyl which is unsubstituted or substituted by nitro chlorine, bromine, methyl, ethyl, methoxy or ethoxy.
 4. The compound of claim 1 wherein Y is cyano, carboxyl, a carboxylic ester group, alkylsulfonyl, CON(CH₃)₂, or COCH₃.
 5. The compound of claim 1, wherein R is a phenyl which is unsubstituted, mono-substituted or poly-substituted by chlorine, bromine, methyl, nitro, methoxy or NHCOCH₃.
 6. The compound of claim 1 wherein R₁ is hydrogen, or a C₁ -C₄ alkyl which is unsubstituted or substituted by cyano.
 7. The compound of claim 1 wherien X is methyl, Y is cyano, R is phenyl and R₁ and R₂ are each ethyl.
 8. The compound of claim 1 wherein X is hydrogen, Y is cyano, R is phenyl and R₁ and R₂ are each ethyl. 